EP0281447A1 - Verfahren zur Herstellung von thermoplastischen, polymerischen Profilen durch Pultrusion, Vorrichtung und hergestellte Gegenstände - Google Patents

Verfahren zur Herstellung von thermoplastischen, polymerischen Profilen durch Pultrusion, Vorrichtung und hergestellte Gegenstände Download PDF

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Publication number
EP0281447A1
EP0281447A1 EP88400287A EP88400287A EP0281447A1 EP 0281447 A1 EP0281447 A1 EP 0281447A1 EP 88400287 A EP88400287 A EP 88400287A EP 88400287 A EP88400287 A EP 88400287A EP 0281447 A1 EP0281447 A1 EP 0281447A1
Authority
EP
European Patent Office
Prior art keywords
fibers
impregnated
die
wicks
rovings
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88400287A
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English (en)
French (fr)
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EP0281447B1 (de
Inventor
Michel Glemet
Alain Causier
Bernard Gourdon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Atochem SA
Elf Atochem SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Atochem SA, Elf Atochem SA filed Critical Atochem SA
Priority to AT88400287T priority Critical patent/ATE65738T1/de
Publication of EP0281447A1 publication Critical patent/EP0281447A1/de
Application granted granted Critical
Publication of EP0281447B1 publication Critical patent/EP0281447B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/521—Pultrusion, i.e. forming and compressing by continuously pulling through a die and impregnating the reinforcement before the die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor

Definitions

  • the present invention relates to a method for manufacturing thermoplastic polymer profiles reinforced with continuous long fibers by pultrusion.
  • the process consists, before shaping the rovings impregnated with thermoplastic resin, to crush said rovings so as to form a sheet of which the elementary fibers of the rovings are impregnated with thermoplastic resin in the molten state.
  • the sheet is formed by passing the rovings, after impregnation of thermoplastic resin, in a flat rectangular heated die so as to crush them thus forcing the molten resin to penetrate between the fibers.
  • the process applies to thermoplastic polymers in general, but it also makes it possible to obtain a new polyvinyl chloride profile reinforced with long continuous fibers.
  • thermoplastic resin profiles by pultrusion.
  • the usual method consists in impregnating resin with the rovings and then circulating the bulk assembly in a heated tunnel, for example with hot air or infrared, at a temperature sufficient to ensure the melting of the polymer.
  • a heated tunnel for example with hot air or infrared
  • the rovings coated with resin enter a heated device making it possible to give the final shape of the product to be produced which is cooled at the outlet of the device.
  • This process has a serious drawback: the difficulty of melting and uniformly distributing the thermoplastic resin at the heart of the rovings.
  • a roving is formed from the union of several continuous elementary fibers.
  • several rovings are impregnated which, passing through the heated tunnel, go loose to join together to form spindles of bundled fibers of high volume.
  • Radiant heating will hardly allow the melting of the thermoplastic resin at the heart of the spindle and its impregnation of the elementary fibers. This lack of homogeneity of impregnation and consequently the trapping of air between the non-impregnated fibers will be a source of defects in the mechanical properties of the final product.
  • the process according to the invention makes it possible in the pultrusion technique to shape rovings in which - the elementary fibers are practically all impregnated with thermoplastic resin after maximum elimination of the air occluded between the fibers.
  • the process consists of impregnating rovings, that is to say continuous wicks of fibers, of thermoplastic resin according to known techniques, circulating the assembly in a heated assembly so as to melt the thermoplastic resin and then conforming to hot the profile in a suitable die to give the profile its substantially final shape before passing it through a second cooled die.
  • the characteristic of the process is to crush the spindles of rovings, that is to say all the wicks impregnated with thermoplastic resin in the heated assembly consisting of a flat die whose flared entry is wide enough to leave the transition to the initial volume of the spindles of rovings, the air gap of variable thickness of the die making it possible to bring out the impregnated assembly in the form of a sheet of minimum thickness before conformation.
  • Figure 1 illustrates a spindle of rovings R themselves made up of the union of several fibers F. These rovings according to the invention are before their meeting in spindles impregnated with thermoplastic resin.
  • the spindles are introduced into the die of Figure 2 through the flared inlet 1 and pulled and crushed in the air gap of variable thickness 2.
  • the ply 3 consisting of fibers impregnated with molten thermoplastic resin, is directed to the known and already cited conformator.
  • the sheet leaving the flat die whose air gap is of substantially rectangular section is in the form of crushed rovings closely linked to each other whose elementary fibers are impregnated with thermoplastic resin. This regular impregnation is the consequence of the crushing allowing on the one hand to increase the heat exchange surface and on the other hand to eliminate to the maximum the air occluded inside the rovings and at their junction.
  • the air gap, of substantially rectangular section is of substantially rectangular parallelepiped geometry on the outlet zone.
  • the alpha connection angle shown in Figure 2, corresponding to the slope of the insertion area between the outside and the horizontal part of the die gap allows to ensure a gradual melting of the surface polymer which plays then the role of lubricant.
  • the length of the introduction zone and the value of the connection angle can vary depending on the polymers considered and the volume of prepreg rovings to be introduced. A length between 35 and 50 mm. and an angle between 1 and 20 ° depending on the case seems particularly suitable.
  • the length of the die must be such that as a function of its temperature, lower than the thermal degradation temperature of the thermoplastic polymer, the latter at the heart of the sheet leaving said die is in the molten state.
  • the thickness of the air gap of the die is adjustable so as to be able to produce sheets of various thicknesses leading to profiles of greater or lesser volume. This thickness adjustment can be done by any means making it possible to play on the spacing of the air gap, for example by screw systems or else by springs making it possible to separate or bring the opposite walls of the die apart.
  • rovings are impregnated according to known techniques, for example by unwinding the rovings in a fluidized bed thermoplastic polymer in the form of a fine powder; it is also possible to coat the rovings by extruding them through a square head die enabling them to be coated with a layer of polymer; Rovings can also be coated with polymer latex.
  • the rovings as already specified, are in the form of continuous wicks consisting of the union of several elementary fibers. These rovings can be formed from mineral or organic fibers, glass fibers, carbon fibers and aramids being most usually used for the reinforcement of plastics.
  • the impregnated rovings, gathered in spindles, are introduced into the die, previously described, heated so as to melt the polymer.
  • the sheet leaving the die, maintained at a temperature such that the polymer remains in the molten state is conveyed to the shaping die giving the sheet the shape of the final profile to be produced.
  • This second die is of course at a temperature sufficient to keep the polymer sufficiently fluid to be transformed. It is not excluded, especially in the case of production of complex or bulky profiles, to subject the web to a progressive pre-shaping before the final shaping.
  • the profile passes through a cooled shaper, the inlet geometry of which is substantially identical to the outlet geometry of the shaping die. The profile is then taken from a drawing bench where it is cut to the desired dimensions.
  • thermoplastic resins reinforced with long continuous fibers The particularly recommended thermoplastic resins can be chosen from polyolefins: high and low density polyethylenes, linear low density, or polypropylene; ethylene-vinyl acetate copolymers; polystyrene, acrylonitrile butadiene styrene (ABS) copolymers, polyvinyl chloride, polyamides 6, 11, 12, 6-6, 6-10, polyesters, poly (ether-amide) block copolymer, fluorinated polymers, polysulfone, polyethersulfone, polycarbonate, thermostable thermoplastic polymers such as polyetheretherketone, polyphenylene sulfide, polyetherimide, polyphenylene oxide, polyphenylene ether or mixtures thereof, the functional thermoplastic oligomers reactive by polyaddition or polycondensation with optionally a coreactant.
  • ABS acrylonitrile butadiene styrene
  • Another advantage of the process is the production of a new product in this case: a profile of substantial cross section of rigid polyvinyl chloride reinforced with continuous long fibers and more particularly with long glass fibers.
  • Low-section polyvinyl chloride profiles reinforced with long fibers are known, but for the reasons given above due to the characteristics of polyvinyl chloride, it has never been possible to produce profiles of substantial section whose length of fibers reinforcement corresponds continuously to the length of the profile.
  • the profiles obtained according to the invention have the characteristic of having a very high rigidity. Furthermore, from such profiles in the form of rods, ribbons or rods, it is possible to cut elements of variable lengths in which the length of the reinforcing fibers corresponds to the length of said elements. These cut elements, once melted, are advantageously transformed by extrusion, injection-compression or compression to preserve the final length of the fibers.
  • the interest lies in a substantial increase in the properties of rigidity, impact resistance, dimensional stability and retention of these properties at high temperatures.
  • the glass fiber rovings are unwound from the outside and then impregnated with polyamide 6 powder (ORGASOL 1002 D) by passage through a fluidized bed.
  • the polymer is melted in a flat die, then the final 10 x 4 mm profile is shaped. is carried out successively in a hot preforming die kept at a temperature of 280 ° C and then in a cooling die kept at 22 ° C.
  • the flat die used for the fusion has the following geometry: . length: 300 mm. . width: 100 mm. . connection angle: 15 ° . length of the insertion area: 35 mm. . air gap: 1 mm. . thickness at die outlet: 0.45 mm.
  • the pre-shaping and cooling systems have a connection angle of 20 ° C over an insertion length of 5 mm.
  • the volume of a glass fiber roving before impregnation is 0.45 x 4.5 mm. about.
  • the roving is in the form of a spindle with a diameter of 8 to 10 mm. about.
  • the output pulling speed is 1 m / Min.
  • the rigidity of the profiles thus produced is measured by a three-point bending method according to standard ASTM D 790.
  • the elastic modulus E and the maximum stress ⁇ are measured.
  • an identical profile is prepared by direct conformation by passing the spindles of rovings impregnated with polyamide 6 through a hot air tunnel so that the resin at the outlet is in the molten state at the heart of the spindles.
  • the mass of fibers coated with molten polyamide 6 is introduced into the shaping die maintained at a temperature of 280 ° C.
  • the profile is pulled into the cooling die maintained at 22 ° C.
  • Example 1 Under the apparatus and process conditions of Example 1, a section of 10 ⁇ 4 mm section is made of polyvinyl chloride reinforced with long continuous glass fibers.
  • the conditions specific to the example are: . polyvinyl chloride powder with average diameter: 100 ⁇ m . quantity of polyvinyl chloride impregnated: 63.1% volume . temperature of the flat die: 200 ° C. . temperature of the shaping die: 190 ° C . cooling die temperature: 15 ° C
  • the flat fusion die has the following geometry: . length: 200 mm. . width: 100 mm. . connection angle: 1 ° . length of the insertion area: 50 mm. . air gap: 1 mm. . die outlet thickness: 0.45 mm.
  • Example 1 Under the apparatus conditions of Example 1 for the comparative test, it was not possible to manufacture the correct long fiber profile. The gelation of the spindles of rovings is insufficient at heart.
  • An increase in the temperature of the hot air tunnel causes thermal degradation of the periphery of the impregnated roving spindle.
  • a section 10 ⁇ 4 mm section is made from a polyamide 11 prepolymer powder with a molecular weight of 4000.
  • the particle size of the powder is between 80 and 200 ⁇ m. 18 rovings R 099 P 103 (VETROTEX) of 2400 Tex were used.
  • the drawing speed is 0.5 m / min.
  • the prepolymer increases in viscosity in situ by heating in the flat die with elimination of water before the shaping die.
  • the geometry of the flat die is as follows: . length: 300 mm. . width: 100 mm. . connection angle: 15 ° . length of the insertion area: 35 mm. . air gap: 1 mm. . die outlet thickness: 0.45 mm.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Moulding By Coating Moulds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Polymerisation Methods In General (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
EP19880400287 1987-02-18 1988-02-08 Verfahren zur Herstellung von thermoplastischen, polymerischen Profilen durch Pultrusion, Vorrichtung und hergestellte Gegenstände Expired - Lifetime EP0281447B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88400287T ATE65738T1 (de) 1987-02-18 1988-02-08 Verfahren zur herstellung von thermoplastischen, polymerischen profilen durch pultrusion, vorrichtung und hergestellte gegenstaende.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8702084A FR2610864B1 (fr) 1987-02-18 1987-02-18 Procede de fabrication de profiles de polymere thermoplastique par pultrusion - appareillage - produits obtenus
FR8702084 1987-02-18

Publications (2)

Publication Number Publication Date
EP0281447A1 true EP0281447A1 (de) 1988-09-07
EP0281447B1 EP0281447B1 (de) 1991-07-31

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EP19880400287 Expired - Lifetime EP0281447B1 (de) 1987-02-18 1988-02-08 Verfahren zur Herstellung von thermoplastischen, polymerischen Profilen durch Pultrusion, Vorrichtung und hergestellte Gegenstände

Country Status (13)

Country Link
US (1) US5084222A (de)
EP (1) EP0281447B1 (de)
JP (1) JP2634184B2 (de)
KR (1) KR930000742B1 (de)
CN (1) CN1023305C (de)
AT (1) ATE65738T1 (de)
CA (1) CA1331910C (de)
DE (1) DE3863943D1 (de)
DK (1) DK168327B1 (de)
ES (1) ES2023497B3 (de)
FI (1) FI95010C (de)
FR (1) FR2610864B1 (de)
PT (1) PT86780B (de)

Cited By (2)

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Publication number Priority date Publication date Assignee Title
EP0544049A1 (de) * 1991-11-28 1993-06-02 Monsanto Europe S.A./N.V. Nylon Pultrusionsverfahren
WO2011156693A3 (en) * 2010-06-11 2012-02-02 Ticona Llc Structural member formed from a solid lineal profile

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AU2008318609B2 (en) * 2007-10-30 2014-01-30 Flsmidth A/S Improved fiber reinforced plastic composites and method and apparatus for making
EP2585279B8 (de) 2010-06-22 2016-07-27 Ticona LLC Thermoplastisches prepreg mit endlosfasern und langen fasern und verfahren zu deren herstellung
WO2011163357A2 (en) 2010-06-22 2011-12-29 Ticona Llc Reinforced hollow profiles
US9409347B2 (en) 2010-06-22 2016-08-09 Ticona Llc Method for forming reinforced pultruded profiles
WO2012142107A1 (en) 2011-04-12 2012-10-18 Ticona Llc Continious fiber reinforced thermoplastic rod and pultrusion method for its manufacture
US9381675B2 (en) * 2011-11-30 2016-07-05 The Boeing Company Stabilized dry preform and method
US9352518B2 (en) 2013-06-21 2016-05-31 The Boeing Company Staggered bevel for continuous compression molding tooling dies
DE102013226730A1 (de) * 2013-12-19 2015-07-09 Airbus Operations Gmbh Imprägnierwerkzeug und Verfahren zum kontinuierlichen Imprägnieren eines Verstärkungsfasermaterials mit einem Kunststoffmaterial
US9827710B2 (en) 2014-02-04 2017-11-28 The Boeing Company Radius filler and method of manufacturing same
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CN104985828A (zh) * 2015-07-02 2015-10-21 北京博简复才技术咨询有限公司 碳纤维复合材料腰带及碳纤维复合材料腰带的制造方法
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CN106009613A (zh) * 2016-06-28 2016-10-12 大连华工创新科技股份有限公司 一种玻璃纤维板材或型材或管材及成型方法
CN106042412A (zh) * 2016-06-28 2016-10-26 大连华工创新科技股份有限公司 一种玻璃纤维板材或型材或管材及成型设备
FR3053914B1 (fr) * 2016-07-18 2019-06-21 Cqfd Composites Procede d’obtention d’une piece profilee en matiere composite thermoplastique, et dispositif de mise en œuvre de ce procede
CN106239939A (zh) * 2016-08-05 2016-12-21 振石集团华美新材料有限公司 一种热塑性复合材料型材的拉挤成型设备及其成型方法
WO2018181239A1 (ja) * 2017-03-27 2018-10-04 日本ゼオン株式会社 ゴム状重合体用押出乾燥機、ゴム状重合体の乾燥方法、およびゴム状重合体の製造方法
KR102334459B1 (ko) * 2017-11-29 2021-12-08 롯데케미칼 주식회사 연속섬유 보강 열가소성 수지 복합재료 및 그 제조방법
CN109049687B (zh) * 2018-09-17 2021-06-22 航天特种材料及工艺技术研究所 3d打印原料及其3d打印方法和3d打印制件
FR3098517B1 (fr) * 2019-07-09 2021-06-04 Arkema France Procede de preparation d’un materiau fibreux impregne par pultrusion reactive
US11951690B2 (en) * 2020-12-31 2024-04-09 Arris Composites Inc. Method for processing massive fiber-composite preforms

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0544049A1 (de) * 1991-11-28 1993-06-02 Monsanto Europe S.A./N.V. Nylon Pultrusionsverfahren
FR2684331A1 (fr) * 1991-11-28 1993-06-04 Monsanto Europe Sa Procede de fabrication d'articles a matrice polyamide, par reaction et pultrusion, et articles obtenus.
US5492755A (en) * 1991-11-28 1996-02-20 Monsanto Company Product formed by a nylon pultrusion process
WO2011156693A3 (en) * 2010-06-11 2012-02-02 Ticona Llc Structural member formed from a solid lineal profile
US20130136891A1 (en) * 2010-06-11 2013-05-30 Ticona Llc Structural Member Formed From A Solid Lineal Profile
US9238347B2 (en) * 2010-06-11 2016-01-19 Ticona Llc Structural member formed from a solid lineal profile
RU2572892C2 (ru) * 2010-06-11 2016-01-20 ТИКОНА ЭлЭлСи Конструктивный элемент, изготовленный из сплошного линейного профиля
US9919481B2 (en) 2010-06-11 2018-03-20 Ticona Llc Structural member formed from a solid lineal profile

Also Published As

Publication number Publication date
ATE65738T1 (de) 1991-08-15
CN88100835A (zh) 1988-08-31
DK81088A (da) 1988-08-19
PT86780A (pt) 1989-02-28
KR880009778A (ko) 1988-10-05
US5084222A (en) 1992-01-28
CA1331910C (fr) 1994-09-13
FI95010C (fi) 1995-12-11
FI880750A (fi) 1988-08-19
FR2610864B1 (fr) 1989-06-16
JP2634184B2 (ja) 1997-07-23
FI880750A0 (fi) 1988-02-17
KR930000742B1 (ko) 1993-01-30
FI95010B (fi) 1995-08-31
DE3863943D1 (de) 1991-09-05
DK168327B1 (da) 1994-03-14
FR2610864A1 (fr) 1988-08-19
ES2023497B3 (es) 1992-01-16
EP0281447B1 (de) 1991-07-31
PT86780B (pt) 1993-08-31
CN1023305C (zh) 1993-12-29
JPS63216732A (ja) 1988-09-09
DK81088D0 (da) 1988-02-17

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